CN105102555B - Fuse metal Nano structure network and the fusion solution with reducing agent - Google Patents
Fuse metal Nano structure network and the fusion solution with reducing agent Download PDFInfo
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- CN105102555B CN105102555B CN201480018734.0A CN201480018734A CN105102555B CN 105102555 B CN105102555 B CN 105102555B CN 201480018734 A CN201480018734 A CN 201480018734A CN 105102555 B CN105102555 B CN 105102555B
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- H—ELECTRICITY
- H03—ELECTRONIC CIRCUITRY
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- H03K17/00—Electronic switching or gating, i.e. not by contact-making and –breaking
- H03K17/94—Electronic switching or gating, i.e. not by contact-making and –breaking characterised by the way in which the control signals are generated
- H03K17/96—Touch switches
- H03K17/962—Capacitive touch switches
- H03K17/9622—Capacitive touch switches using a plurality of detectors, e.g. keyboard
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- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- G06F3/0445—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means using two or more layers of sensing electrodes, e.g. using two layers of electrodes separated by a dielectric layer
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Abstract
Present invention has discovered that sparse metal nanowire film is effectively chemically solidified into fusion metal Nano structure network by reducing/oxidizing reagent via obvious maturing type process.Gained fusion network can provide required low sheet resistance while maintain good optical transparency.Nesa coating effectively can be applied in the form of single conductive ink or be sequentially formed metal nanowire film via under follow-up addition fusion agent to apply.Fusion metal nanowire film can be effectively patterned, and patterned film goes for the device of such as tactile sensor.
Description
Technical field
The present invention relates to fusion nanostructured metal network.Moreover, it relates to will using oxidant and/or reducing agent
Metal nanometer line fuses into the fusion method of nanostructured network.Fusing nanostructured metal network can be saturating effective for being formed
Bright conducting film.
Background technology
Functional membrane can provide critical function in a series of situations.For example, conducting film is for possible in electrostatic
Can be important for static dissipation when being bad or dangerous.Optical film may be used to provide various functions, such as polarizes, be anti-
Reflection, phase shift, brightness enhancing or other functions.High quality display can include one or more optical coatings.
Transparent conductor can be used for several optoelectronic applications, including for example touch-screen, liquid crystal display (LCD), flat board show
Show device, Organic Light Emitting Diode (OLED), solar cell and intelligent window.In history, tin indium oxide (ITO) because its
Of a relatively high transparency under high electrical conductivity and turn into selected materials.However, there are several deficiencies in ITO.For example, ITO
It is the brittle ceramic for needing to use sputter to deposit, sputter is a kind of manufacturing process for being related to high temperature and vacuum, and therefore relative
It is slower and not cost-effective.Additionally, it is known that ITO is easy to ftracture on pliability substrate.
The content of the invention
In the first aspect, the present invention relates to a kind of method for forming fusion metal Nano structure network, methods described bag
Contacted containing metal nanometer line is made with fusion solution.In certain embodiments, fusion solution includes reducing agent source and metal ion
Source.Metal ion is effectively reduced into its respective metal element by contact procedure, so as to by metal nanometer line fuse together with
Form fusion metal Nano structure network.
In other side, the present invention relates to a kind of method for forming fusion metal Nano structure network, methods described bag
Metal nanowire film on the substrate surface containing radiation fuses metal Nano structure network to be formed.
In another aspect, it is used to metal nanometer line fusing into conductive fusion metal Nano structure the present invention relates to one kind
The fusion solution of network, wherein the fusion solution includes metal nanometer line, metal ion source and reducing agent and/or oxidation
Agent.
In another aspect, the present invention relates to one kind to fuse metal Nano structure network, and it includes fusion metal nanometer line
Fragment, form the conductive network for being substantially free of halide.In certain embodiments, fuse metal nanometer line fragment and include first
Metal composites, it is fused with the second metal composites identical or different with the first metal composites is received with forming fusion metal
Rice structural network.
Moreover, it relates to a kind of solution group for sequentially applying, the solution group includes nano wire ink, and (it is wrapped
Dispersion liquid containing metal nanometer line) and fusion solution.Fusion solution can include metal ion source and reducing agent and/or oxidation
Agent, wherein fusion solution effectively fuses the film of metal nanometer line when drying.
In other embodiments, the present invention relates to a kind of patterned transparent conductive material, it includes substrate, covering substrate table
The fusion metal Nano structure network of the part in face and substrate surface are substantially free of metal nanometer line and fusion wire netting
The region of network.Fusion metal Nano structure network can form conductive pattern.In certain embodiments, transparent conductive material is total
Transmission of visible light is at least about 91%.For patterned transparent conductive material, tactile sensor can include the first electricity
Pole structure and the second electrode structure opened in configuring naturally with first electrode spacing structure, the first electrode structure is first
The first transparent conductive electrode is included on substrate, wherein first transparent conductive electrode includes patterned transparent conductive material.
Brief description of the drawings
Figure 1A is the schematic diagram for the sintering network that displaying forms the conductive pattern with single-pathway along substrate surface.
Figure 1B is the signal for the sintering network that displaying forms the conductive pattern with multiple conductive paths along substrate surface
Figure.
Fig. 2A is the schematic diagram for showing the tactile sensor based on electric capacity.
Fig. 2 B are the schematic diagrames for showing the tactile sensor based on resistance.
Fig. 3 is the logarithmic scale figure of the resistance data of the film 1-10 from example 1.
Fig. 3 a are the conjunctions for the SEM image that the AgNW films surface of membrane sample 5 in representative instance 1 gathers under different amplification
Cheng Tu.
Fig. 4 is the logarithmic scale figure of the resistance data of the film from example 2 before and after sintering solution is applied.
Fig. 4 a are the SEM images on the surface of the AgNW films of film 1 and 2 in representative instance 3.
Fig. 5 is the atomic force microscopy image with the sample P d3 of the example 7 AgNW networks formed.
Fig. 5 a are the conjunctions for the SEM image that the AgNW films surface of sample P d1 in representative instance 7 gathers under different amplification
Cheng Tu.
Fig. 6 is the atomic force microscopy image of the AgNW networks formed with dilute copper-containing solution of example 8.
Fig. 6 a are the synthesis for representing the SEM image that the AgNW films surface of sample 1 in table 11 gathers under different amplification
Figure.
Fig. 6 b are to represent the SEM gathered under different amplification with the AgNW films surface of the CT2 films formed in table 12 to scheme
The composite diagram of picture, but the sheet resistance of the AgNW films is about 200 ohm-sqs.
Fig. 7 is the atomic force microscopy figure of the AgNW networks formed in the case where example 12 is sintered based on benzoic solution
Picture.
Embodiment
Fusion metal Nano structure network is described as having compared with low resistance and high light transparency, and it can be used
Through being found that the redox equilibrium system for fusing network formation can be driven to be formed.In addition, fusion can be driven by curing process
Dynamic, in curing process, material can undergo the net transfer of material between position to reduce free energy.In certain embodiments,
The metallic element that the fusion abutment of nanostructured can include the metal nanometer line component from being incorporated in fusion structure is different
Metal element.Exactly, fusing agent solution can be formed with the admixture of acid and reducing agent, and the reducing agent is selected to
Metal ion in reducing solution is so as to forming the fusion abutment of nanostructured.Special metal ion can be introduced into for
Metal element is reduced into, so as to form fusion metal Nano structure network.In other or alternate embodiment, oxygen can be provided
Agent (such as appropriate acid solution) is using from fact as discharging in the metal nanometer line component of unique metal ion source
Metal ion, so that metal nanometer line can provide metal ion with itself, the metal ion is reduced to fuse gained nanometer
Abutment in structure.The discovery that chemical reducing agent can form the fusion junction surface of metalolic network provides following ability:
New construction is formed, and provides and is used for the alternative side that metalolic network is formed in addition to the halide ion fusion mechanism previously found
Method.Based on reducing agent is used as into fusion agent, nanostructured metal network can be formed, wherein junction point metal can have with
The metallic element that the metallic element of component metals nano wire for forming the structure is different forms, and in some applications
These hybrid structures may be needed.
Method is described as effectively handling gold with selected structure and appropriate reducing agent and acid (it can be oxidant)
Belong to nanometer line network.Fusion solution can merge with metal nanometer line dispersion liquid handles fusion gold that can realize by single ink
Belong to nanostructured network., can be by comprising reducing agent and/or optional metal cation in other or alternate embodiment
Fusion solution is added in deposited metal nanowire film.Via the selected deposition of fusion solution, figure can be effectively carried out
Case, wherein highly conductive region have fusion metalolic network, and the region of low conductivity is not positioned at carrying out fusion.Due to
Good electric conductivity and optical clarity, fusion metal Nano structure network are completely suitable for forming transparent conductive electrode, such as
For appropriate display, sensor, photovoltaic cell etc..
In order to form stablizing solution, it usually needs including acid and reducing agent so that the metal ion in fusion solution will not
It is nucleated and forms particle.Although when there may be the side that handles the structure when in the case of anaerobic agent using a variety of solution
Formula, but processing is generally based on the substantial equilibrium of oxidation-reduction system.When being combined with the metal nanometer line in film, the oxygen of balance
Change reduction (redox) system and lure metal net migration into the junction surface between adjacent nano wire to fuse the junction surface.For
Metal nanometer line is fused into this redox driving mechanism of nanostructured network be found to be to be formed fusion metal nano knot
Network forming network provides extra flexibility and processing selects.Form the observation of the driving force of fusion network and in metallic atom mobility
The similar driving force observed in the case of being induced by the metal halide being coated on above metal wire is consistent.Additionally, it is to be noted that
Metal ion can be provided in fuse in solution or can be formed by etching line.Removable ion is diffusible and can be
Reduced at junction surface between nano wire, cause free energy to reduce.The net change produced in the material of fusion nanostructured is class
Ostwald ripening process (Ostwald ripening process) is similar to, wherein anti-for current maturing process, redox
The mobility of material should significantly be driven to provide relatively quick maturing type process.
Metal nanometer line can be formed by a series of metals.For example, a series of manufacture of metal nanometer lines is for example retouched
Be set forth in the city wall island (Miyagishima) being incorporated herein by reference et al. it is entitled " metal nanometer line, for producing
Method and transparent conductor (Metal Nanowires, Method for Producing the Same, and of the nano wire
Transparent Conductor) " U.S. Patent Application Publication 2010/0078197 in.Nano silver wire due to silver compared with
High conductivity and be particularly subject to pay close attention to.On the specific manufacture of nano silver wire, see, for example, the entitled " silver nanoparticle in city wall island et al.
Line, its production method and aqueous liquid dispersion (Silver Nanowire, Production Method Thereof, and
Aqueous Dispersion) " U.S. Patent Application Publication 2009/0242231, and horizontal well (Hirai) et al. is entitled
" nano silver wire, its production method and aqueous liquid dispersion (Silver Nanowire, Production Method Thereof,
And Aqueous Dispersion) " U.S. Patent Application Publication 2009/0311530, and U.S. of king (Wang) et al.
Patent 7,922,787 " is used for method (the Methods for the Production of Silver for producing nano silver wire
Nanowires) ", all three applications are incorporated herein by reference.
Although metal nanometer line is inherently conductive, it is believed that most resistance in the film based on nano silver wire are attributions
Junction surface between nano wire.Depending on treatment conditions and nano wire property, such as the nano wire film of relative transparent deposited
Sheet resistance may greatly, such as in Giga-ohm range or even more high.It is proposed do not destroying optical clarity
In the case of reduce nano wire film resistance various methods.As described herein, it has been found that for forming metal Nano structure network
Low temperature fusable extremely effective reduce resistance while maintain optical clarity.
Remarkable break-throughs on realizing the conducting film based on metal nanometer line are to find a kind of neighbour for forming metal nanometer line
Connect partially fused fusion metalolic network.Exactly, it has been found that in Previous work, halide ion can drive metal to receive
The low temperature fusable of rice noodles is to form fusion metal Nano structure.Fusion agent comprising halide anion introduces in a variety of ways, from
And successfully realize and accompany by the fusion that resistance accordingly drastically declines.Exactly, the fusion of metal nanometer line and halide anion
Realized with steam acid halide and with the solution of halide salts or sour halide.
It is believed that strengthening mobility/diffusivity of metal ion along the metal halide on metal nanometer line surface, it causes
The fusion of contact or proximity contact between nano wire is to form fusion network.Evidence suggests work as to use halide fusion agent
When, metal halide shell is formed on gained fusion nanometer line network.While not wishing to bound by theory, it is believed that metal nano
Metal halide coating on line causes the metallic atom from nano wire/ion to move and causes mobile ion condensation so that shape
Abutment between neighbouring nano wire, forms nanostructured network, and may be moved only in nanostructured in metallic atom
Free energy is reduced when fusion network is formed in the case of dynamic.
On processing, the fusion of metal nanometer line and halide anion using exposed to sour halide vapor continue compared with
Short time period, by the way that halide is fused, solution is sprayed in metal nanowire film and generation fuses after deposition and drying
Successfully realized in the case that the ink comprising metal nanometer line and halide fusion agent of metal Nano structure network is formed.
Fuse metal Nano structure network has than incomplete fusion nano wire film while good optical transparency is maintained and compared with low turbidity
The electric conductivity of big at least several orders of magnitude.The use of halide anion fusion agent is described in detail in dimension card (Virkar) et al. 2012
Entitled " metal nanometer line network and transparent conductive material (Metal Nanowire Networks filed on June 22, in
And Transparent Conductive Material) " U.S. Patent application 2003/0341074 (" application of ' 074 "),
With dimension card et al. entitled " metal Nano structure network and transparent conductive material (Metal filed in 30 days October in 2012
Nanostructured Networks and Transparent Conductive Material) " disclosed United States Patent (USP)
Apply in 2013/0342221 (" application of ' 221 "), the application is incorporated herein by reference.The application of ' 221 is also discussed
The method of merging method can be now considered as by stating, wherein the silver fluoride being dissolved in ethanol is applied as fusion solution.As herein
It is described in detail, in the solution of merging, fluorine ion can effectively form metal fluoride (example with itself on metal nanometer line
Such as silver fluoride) shell is to promote metal migration so as to fuse adjacent nano wire, and ethanol can be with the silver ion in reducing solution
So as to also fuse adjacent nano wire.Now understanding these fusion solution can induce to form two kinds that fuse metal Nano structure network
Mechanism.
As described herein, it has been found that fusion nanostructured metal network can be formed via redox machinery, described
Redox machinery is a kind of to look extremely different mechanism from halide driving mechanism that is previously finding.Exactly,
It is found that reducing agent and/or oxidant provide driving force so that for producing the molten of metal nanometer line from the metal ion of solution
Close, so as to form fusion metal Nano structure network.For the purposes of reducing agent, metal ion is generally in the solution as sun
Ion source is for being reduced into metal element.It has been found that the metal being reduced effectively fuses contiguous metal nano wire, from
And fusion metal Nano structure network needed for being formed.Metal ion for reduction can be via selected by the addition into fusion solution
Metal salt and introduce or introduced via metal ion is formed in situ from metal nanometer line component.Exactly, to fusion solution
Middle addition oxidizing acid can etch metal nanometer line to form the metal cation of metal nanometer line metal.Oxidant can also be put down
Weigh reducing agent, so as to the stable fusion solution under the conditions of more in check and/or driving fusion reaction.In addition, fusion solution can
To provide or produce metal ion, the metal ion can online between intersection or close contact at reduction and will knot
Structure fuses together.
Fusion solution generally comprises the reducing agent for inducing fusion and can further include metal ion source and/or gold
Belong to nano wire.Acid is applicable to fuse solution to help to dissolve or partly remove the nano wire from nano wire synthesis technique
On polymer coating, and oxidizing acid is applicable to buffer current potential to control depositing operation and stable fuse solution.Definitely
Say on ground, it usually needs include metal ion source in fusion solution so as not to deposit severally with each of metal ion source
Other solution.However, for metal nanometer line, it may be necessary to or may not be needed first by metal nanometer line deposit film forming and
Then fusion process is performed via addition fusion solution.If single solution is used together with metal nanometer line with fusion agent,
So it may need not long ago to form solution in use when metal nanometer line can be fused other components etching of solution.As above
Described, reducing agent is probably or may not be solvent, and it correspondingly will exist with higher concentration.Metal source can be dissolved in
Metal salt in solution or the oxidant by metal nanometer line generation metal ion.
The source of metal ion in solution is not considered, and reducing agent can be effectively in the junction of contiguous metal nano wire
The place's of putting deposited metal is to fuse contiguous metal nano wire, so as to form fusion nanostructured network.In addition, once exist metal from
Son, it can be diffused into the region between nano wire, and can be reduced at the junction surface between nano wire, and this causes electrification
The curing of Ovshinsky type is learned, because the deposition in junction point can be thermodynamically more favourable than the deposition along line fragment.Add
The metal salt being added in fusion solution can be included relative to the original metal nano wire identical metal member being added in network
Plain or different metallic element.In this way, the abutment for fusing nanostructured network can be initial in network comprising being incorporated to
The identical or different metal of metal nanometer line component.As further discussed below, in certain embodiments, abutment may need
To be formed by the different metal of the metal nanometer line component from being fused in nanostructured.
Suitable reducing agent should be able to drive metal ion to be reduced into its element form:Ma+→M0, wherein M is selected metal,
" a " is the oxidation state and M of metal cation0Indicate the element form of metal.It has been found that weak reductant (such as some organise
Compound) it may be enough to drive fusion process.For example, alcoholic solvent (such as ethanol) can drive the molten of at least some metals
Close.The metal that result herein shows to be reduced is easy to junction point of the preferential deposition in contiguous metal nano wire, so as to just
Metal Nano structure network is fused in being formed.Selected reducing agent can be in high concentration, such as the group as solvent or solvent mixture
Divide or as the solute under selected concentration.Various alcohol may be used as the suitable reducing agent for silver, palladium and copper.Definitely
Say, find ethanol and propane diols can effectively reducing metal to form fusion metalolic network.Alcohol can be oxidized to aldehyde/ketone or carboxylic
Acid, while correspondingly reducing metal cation.Or other reducing agents can be added into fusion solution with debita spissitudo and (such as had
Machine or inorganic reducing agent).
The system of merging can be related to the fusion solution comprising metal halide and reducing agent.It was observed that these systems are molten
Metal halide shell is formed above alloy category nanostructured network.These systems can probably make junction surface via one kind or two
Kind mechanism fusion.
For fusing in the case of the metal ion of metalolic network provides by metal nanometer line component, fusion solution is usual
Include both Oxidizing and Reducing Agents.For the in-situ preparation of metal cation, oxidizing acid (such as nitric acid) can be used for losing
Metal nanometer line is carved and (aoxidized) to produce metal cation.Acid be equally applicable to remove may be related to metal nanometer line
From any residual polymer of its synthesis, obtained such as in the form of commercial samples.Oxidizing and Reducing Agents in solution be present certain
Redox (redox/reduction-oxidation) current potential of the system is buffered in meaning, and reductant-oxidant can
To realize required result through balancing.Excessive oxidant can be etched more than required metal, and strong oxidizer excessively can make
Metal reduction is quenched so that may not fuse.If Oxidizing and Reducing Agents reasonably balances, then etching metal with to
Metal ion is provided in solution, and reducing agent reducing metal ion is significantly excellent with formation element metal, the metal element
First accumulate in the junction point of contiguous metal nano wire.During maturing process, metal gradually migrates molten to be formed from metal wire
Close junction surface.Thus, it is seen that migrated from the metal nanometer line fragment of lattice to the clean metal of network junction point.While not wishing to
Bound by theory, but this observation result is forcefully prompted free energy to move to abutment from institute's junction fragment via metal and subtracted
It is small.Fusion speed can be influenceed by the balance of Oxidizing and Reducing Agents.The process can be at fusion metalolic network abutment
Required degree fusion after be suitably quenched.Being quenched can be for example real via drying, flushing, dilution or series of processing steps
It is existing.
Sum it up, effective fusion of the metal nanometer line based on metal oxidation reduction mechanism specifically described herein is related to molten
The metal ion and oxidant and/or reducing agent of notable concentration are introduced in liquid.Each activator generally induces reaction, described
Reaction is typically reversible, causes and is ionizing the migration of the metal under mutually being converted with element (i.e. non-ionic) form.Curing
Process causes net migration to fuse metal Nano structure network.Metal ion can be added to fusion solution in, or metal from
Son can be produced by metal nanometer line its home position.The reducing agent that reducing agent can be solvent and/or be added in fusion solution.
Contemplate at this in framework, can successfully use a series of processing methods.In addition, fusion mechanism can be used for easily along lining
Basal surface will fuse metal Nano structure network pattern.The fusion realized with reduction can be used for being effectively formed with good saturating
Lightness and the conducting film compared with low turbidity.
As described above, can be produced for the metal ion for forming fusion junction surface by nano wire starting ingredient itself, or
Metal ion can be added in solution.Metal ion in solution can include the metal nanometer line with synthesis network fusion
Identical element, so that the fusion abutment of network has and nano wire identical metal.It is however, golden via being added into solution
Belong to ion, the metal of deposition can be the metal members different from the metallic element in the presence of original metal nano wire parent material
Element.May need formed fusion network junction point using different metal using potentially reduce use fuse network as
The effect of metal electro-migration during conducting film.Fusion solution can similarly include the mixture of metal ion, the metal from
Son may or may not be reduced with phase same rate self-dissolving liquid.In general, fusing metal Nano structure network can include relatively
Fusion abutment is formed in the identical or different metal of core metal of fusion network.Shape is removed by reducing from the metal of liquid deposition
Into abutment nanostructured lattice can also be coated with to fuse beyond network.
Contrasted relative to the Previous work for being related to halide ion driving metal nanometer line fusion, it is contemplated that by reducing agent driving
Fusion be not generally formed core_shell structure so that fusion metal Nano structure network specifically described herein in this regard with previously
Described fusion network is different.Itd is proposed core-metal halide shell structurre because metal halide reflectivity is relatively low can
Influence the optical property of metalolic network, thus fusion metalolic network specifically described herein can provide it is slightly different optical
Matter.It is believed that compared with the method based on incomplete fusion metal nanometer line network, can compared with low metal (such as metal nanometer line) load capacity
With the successfully conductance needed for realization under fusion.Reducing the ability of content of metal in network can allow to be identical thin layer
The preferable overall optical property and pattern of nanostructured metal network are fused when comparing under resistance compared with non-fusing system
The preferable contrast of conductance in change system.In addition, as described above, metal can be related to being received comprising metal from fusion solution reduction
The different metallic element of rice noodles parent material, so that metal composite structure can be formed relative to fusion metalolic network, it is described
Fusion metalolic network be related to along fusion junction point different metal and can be with the other parts of overlay network.Therefore, use
The fusion metalolic network that reducing agent is formed can have a variety of difference relative to the fusion metalolic network formed with halide ion.
However, the fusion metal Nano structure network formed with reducing agent can have satisfactory electrical conductivity and good optical saturating
Lightness, this is common in the case of the fusion metalolic network formed using halide ion.Improved fusion/sintering specifically described herein
Metal nanometer line network can realize required relatively low sheet resistance value simultaneously while provide good light transmission.In some embodiments
In, fusion metal nanometer line network can have at least 85% light transmission under 550nm wavelength lights, while have less
In the sheet resistance of about 100 ohm-sqs.Light transmission is removing the contribution situation of substrate in the specification and in the claims
Under refer to, and the result provided in examiner is illustrated in instantiation.In other or alternate embodiment, metal is fused
Nanometer line network can be with least 90% light transmission at 550 nm and the thin-layer electric no more than about 250 ohm-sqs
Resistance.Based on good optical transparency and the ability of relatively low sheet resistance is realized simultaneously, fusion metal nanowire film can be effectively
As transparency electrode for a series of applications.The load capacity of the nano wire for forming network can be selected to realize required property
Matter.
Processing can be directed to use with fusing the agent single solution or ink that are combined with metal nanometer line, or can use can be according to
A variety of solution of sequence deposition.In certain embodiments, can be as needed by metal nanometer line, metal ion source and reducing agent
It is combined in two or three of solution out of the ordinary.The larger control to technique, such as control process can be introduced using a variety of solution
Time provides patterning.Various processing schemes described in detail below.For patterning, metal nanometer line can form film,
And selected location can be administered to along nano wire film by fusing solution, so as to by the film process at selected location into fusion nanometer
Structural network leaves other positions as incomplete fusion film simultaneously.Fusion film can have extremely significantly lower electricity compared with incomplete fusion film
Resistance so that pattern is formed by conductive region and electric insulated region.Patterned film can be used for such as tactile sensor etc.
Functional devices.
The nesa coating formed by fusion nanostructured metal network is suitable to various applications.For example, some sun
Battery is designed to have electrode along optical receiving surface, and may need transparent conductive electrode along this surface.In addition, can
To manufacture some display devices with transparent conductive electrode.Exactly, touch input transparent can be led with specifically described herein
Electrolemma is effectively formed, and the effective patterning for fusing nano wire film can be used for forming corresponding pattern touch sensing
Device.As described further below, touch input or sensor be typically based on capacitance variations at feeler surface or
Resistance variations operate.Therefore, processing method specifically described herein can be directed to form nesa coating and provide and significantly commercially should
The property used.
It has been found that fusion nanostructured metal network can be provided in terms of electric conductivity relative to incomplete fusion homologue gold
Belong to the higher contrast of nano wire film, this provides powerful method to be added via the patterning of fusion agent to pattern these films.
This relevant with fusion network finds to allow the machine via similar patterning function is provided for fusing other methods of nano wire
Meeting.Exactly, the fusion based on radiation can be transmitted using patterned radiation to carry out.Can to substrate without excessive damage
In the case of selective radiation come nano wire fusion needed for carrying out.Exactly, infrared light can be because of the reasonable absorption of metal and poly-
The relatively low absorption of compound substrate and as being used to fuse the required source radiation of nano wire.Therefore, patterning method can be extended
To fuse agent and radiation including the fusion agent based on halide, based on redox, it each can effectively provide pattern, institute
State pattern have for fusing the electric conductivity between incomplete fusion region higher contrast and it is conductive with non-conducting areas it
Between there is relatively low visible difference.
Metal nanometer line and fusion solution
By three kinds of components, metal nanometer line, reducing agent and metal ion source are put together to be received with forming fusion in film
Rice structural metal network.In general, fuse acid of the solution generally also comprising debita spissitudo with stablizing solution, relax reaction and
Metal nanometer line is etched in certain embodiments to provide metal ion.Membrane component is delivered to selected substrate surface.Component can
To be transmitted in one or more single solution for being administered to substrate surface.Exactly, it may be necessary to nano wire film is formed, to
The nano wire film addition fusion solution.Suitable metal ion source can include directly needed for offer metal ion for
The metal salt of respective metal is reduced into, or aoxidizes the metal from metal nanometer line as metal ion source for fusion net
The oxidant of network.Provided that metal salt, then metal ion may relate to or may not be related to and metal nanometer line identical
Metallic element.
In general, nano wire can be formed by a series of metals, for example, silver, gold, indium, tin, iron, cobalt, platinum, palladium, nickel,
Cobalt, titanium, copper and its alloy because of high electrical conductivity but needed for.Commercial metals nano wire is available from blue nanometer company (Blue
Nano) (North Carolina (North Carolina, U.S.A)), shell technology company (Seashell
Technologies) (California, USA (California, U.S.A)) and Kechuang advanced material company (KeChuang
Advanced Materials) (China).Silver especially provides fabulous electric conductivity, and commercially available nano silver wire is obtainable.
In order to good transparency and compared with low turbidity, it is necessary to which nano wire is with smaller range diameter.Exactly, it is necessary to metal nano
Line has no more than about 250nm, in a further embodiment no more than about 150nm and is that about 10nm is arrived in other embodiments
About 120nm average diameter.For average length, it is contemplated that the nano wire with long length can provide preferable in network
Electric conductivity.In general, metal nanometer line can have at least 1 micron, in a further embodiment at least 2.5 microns and
About 5 microns to about 100 microns of average length in other embodiments, but the improved synthetic technology of following exploitation can cause
Longer nano wire is possibly realized.Aspect ratio can be designated as the ratio of average length divided by average diameter, and in some implementations
In example, nano wire can have at least about 25, in a further embodiment about 50 to about 5000 and in other embodiments about
100 to about 2000 aspect ratio.Those of ordinary skill in the art are it will be recognized that nano wire chi more than in clear and definite scope
In very little other scopes are covered in and in this disclosure.
The formation of metal nanometer line network, which includes, to be formed described in dispersion liquid and general of the metal nanometer line in suitable liquid
Dispersion liquid is administered on selected substrate surface as coating.The concentration of dispersion liquid can be selected to divide to obtain the good of nano wire
Dissipate, so as to provide the required uniformity of gained coating.In certain embodiments, coating solution can include at least about 0.005 weight
% is measured, in other embodiments about 0.01 weight % to about 5.0 weight % metal nanometer lines, in certain embodiments about 0.02 weight
% is measured to about 4 weight %, and about 0.05 weight % to about 2.5 weight % metal nanometer lines in other embodiments.Affiliated neck
Domain skilled artisan will realize that, in other scopes of the metal nanometer line concentration more than in clear and definite scope are covered in
And in this disclosure.Similarly, can select for forming the liquid of dispersion liquid to obtain good point of nano wire
Dissipate.For example, water, aqueous solvent, alcohol (such as ethanol, isopropanol or isobutanol), solvent (such as the Methylethyl based on ketone
Ketone), organic coating solvents (such as toluene or hexane) etc. or mixture be typically metal nanometer line fine dispersion agent.For
Metal nanometer line is deposited to be initially formed the embodiment of film before being contacted with fusion solution, in the liquid of selection dispersing nanowires
There may be larger flexibility in terms of body, because liquid and need not be compatible with fusion process or fusion agent.
Fusion solution generally comprises reducing agent, metal ion source, and generally comprises sour (it can be oxidizing acid).It is molten
Closing solution can combine with metal nanometer line to form single solution for formation nesa coating, or fusion agent can be severally
Using.The combination of various solvents and solvent can be used for fusion solution specifically described herein.Following table provide a series of solvents with detail
The property for the solvent carefully summarized, and other solvents are included in such as methanol, butanediol, hydroxypropanone-, its mixture and following table
The mixture of listed solvent in the mixture and table of solvent.
In certain embodiments, metal salt or its combination can be included by fusing solution.In general, the metal ion in salt
Can be the metallic element identical metallic element or different metal element with nano wire.In general, metallic element can root
Selected according to needs and corresponding to the metal with satisfactory electrical conductivity.Suitable metal ion includes such as silver ion (Ag+), copper
Ion (Cu+2), gold ion (Au+3), palladium ion (Pd+2), lead ion (Pb+2), aluminium ion (Al+3), nickel ion (Ni+2Or Ni+3)、
Cobalt ions (Co+2Or Co+3), zinc ion (Zn+2), iron ion (Fe+2Or Fe+3), tin ion (Sn+2Or Sn+4) or its mixture.One
As for, the salt can include halide anion, such as (AgF), or with solubility needed for providing or reactivity it is cloudy from
Son.Suitable anion can include alkali (such as acetate), trifluoromethayl sulfonic acid root (TMS), the hyptafluorobutyric acid root of carboxylic acid
(FHB) and hexafluoroantimonic anion (HFA), its combination etc..The anion can correspond to oxidizing acid (such as nitrate anion, high chlorine
Acid group and/or sulfate radical) with for fusion solution provide needed for functional group.
For metal ion, fusion solution can include normally about 0.000001M to about 1M, in a further embodiment
About 0.0001M obtains metal ion to about 0.00001M to about 0.01M to about 0.1M and in other embodiments.Metal ion can be with
It is in situ via the oxidation of metal nanometer line to produce.If metal nanometer line mixes before substrate is administered to fusion solution,
So solution will can merge to avoid the over etching of metal nanometer line before use.The ordinary skill people of art
Member is it will be recognized that other scopes of the concentration of metal ions more than in clear and definite scope covered in interior and are in this announcement
In appearance.
Acid can be included to adjust acid concentration or pH value by fusing solution, and it assesses alcoholic solution in certain embodiments.Acid is dense
Degree/pH value may influence reduction potential, the solubility of reactant, stability of solution and other properties.In general, solution is fused
With the pH value adjusted via addition acid, and pH value can be about 0.5 to about 6, be about 1 to arrive about in a further embodiment
5.5 and be about 1.5 to about 5 in other embodiments.For acid concentration, sour (such as strong acid) can be generally with least about
0.000001M, in a further embodiment about 0.0000025M to about 0.05M and in other embodiments about 0.000005M
Concentration to about 0.01M is added.Acid can also at least remove the polymer that can be coated with commercially available nano wire, such as polyvinylpyrrolidine
Ketone (PVP).Suitable acid can include weak oxide acid (i.e. from H+The appropriate oxidation activity of ion), such as HCl, phosphoric acid, carboxylic
Acid or its combination.Suitable Strong oxdiative acid generally reduces pH value and provides the notable oxidant based on anion simultaneously, and it can be with shadow
Ring the current potential in fusion solution and can be used for etching metal nanometer line as metal ion source.Suitable Strong oxdiative acid bag
Include such as HNO3(nitric acid), H2SO4(sulfuric acid), HClO4(perchloric acid), its mixture etc..Those of ordinary skill in the art
It will be recognized that other scopes of the pH value and acid concentration more than in clear and definite scope covered in and be in this disclosure
It is interior.
Reducing agent can provide as solvent and/or as the additive of solvent.For example, some alcohol are applicable goes back
Former agent.For fusion solution specifically described herein, suitable alcohol include for example methanol, ethanol, isopropanol, isobutanol, 2- butanol,
Propane diols, sugar and its mixture.Ethanol can be oxidized to form acetaldehyde or acetate while metal ion is reduced into element
Metal, and other alcohol can similarly be aoxidized when serving as reducing agent.There is provided in reducing agent as additive into solvent
When, a variety of organic and inorganic compound can be used.In general, based on the stable fusion solution of needs, the reducing power of compound
May be not extremely strong.On the other hand, reducing agent, which must arrive by force, is enough silver-colored and/or other metals under the conditions of fuse step
Ion reduction is into metal element.Inorganic and organo-metallic compound (being usually metal salt and compound) can dissolve in molten at it
Used when closing in solution solvent.Applicable salt includes such as nitrate or sulfate and metal ion (such as V2+、Fe2+、Cr2+、
Sn2+、Ti3+Etc.) misfit thing.Other inorganic reducing agents suitable for fusing solution are oxidisable anion (such as sulfurous acid
Root, bisulfite, thiosulfate anion, orthophosphite, phosphorous acid hydrogen radical, oxalate etc. or its combination) alkali metal salt, ammonium
Salt or other salt.In addition, the nanoparticle suspension of reducing metal (such as zinc, iron, aluminium, magnesium etc.) can be used as reduction in right amount
Agent.Suspension can contain stable material (such as surfactant or dispersant) in addition to help nano-particle to be dispersed in solution
In.Organic reducing agent may be especially useful for the present invention (in addition to the person that also functions as solvent).Suitable organic reducing agent is included (but not
It is limited to) phenolic compound, such as phenol, amino-phenol, quinhydrones, pyrogallol, catechol, phenidone, 4- amino -3- hydroxyls
Base -1-naphthalene sulfonic aicd etc.;Polyalcohol, including sugar alcohol;Sugar, such as monose and disaccharide;Azanol and derivative;Aldehyde;Alpha-hydroxy carbonyl
Compound, such as hydroxy-ketone, such as styrax, furoin, oxyacetone;Hydrazide derivatives, such as phthalylhydrazine, adipic acid two
Hydrazides, phenidone etc.;Reproducibility aromatic compound, such as 1- methyl isophthalic acids, 4- cyclohexadiene, dihydro diazine etc.;And its
Combination.In general, reducing agent can about 0.001mM to about 1000mM, about 0.01mM is to about in a further embodiment
100mM and in other embodiments about 0.1mM obtain concentration to about 10mM and are incorporated to fusion solution, and required concentration generally by
The influence of the chemical property of selected reagent or agent combination, and those of ordinary skill in the art can be by rule of thumb based on herein
Middle teachings assess these problems.Those of ordinary skill in the art are it will be recognized that reduction more than in clear and definite scope
In other scopes of agent concentration are covered in and in this disclosure.If organic additive is supplied in the form of reducing agent
Should, then various solvents can be it is suitable, such as isopropanol, isobutanol, formaldehyde, acetone, other ketone, other aldehyde, its mixing
Thing etc..
Form the program of fusion metalolic network
Fusion nanostructured metal film is usually located on selected substrate surface.The formation of film generally comprises deposition precursor body fluid
Body and fusion.Single liquid can be deposited to form metalolic network, or plurality of liquid, one of which dispersion liquid bag can be used
Containing metal nanometer line, the metal nanometer line can be deposited and then be fused with fusion agent.Handled with single liquid usual
It is related to solution of the deposition with scattered metal nanometer line, metal ion source and reducing agent.Handled with plurality of liquid and generally related to
And on the whole still comprising be isolated in two or more liquid for transmission metal nanometer line, metal ion source
With the liquid of reducing agent.Processing step is reduced using single liquid, and it is extra flexible to provide some using a variety for the treatment of liquids
Property.For example, if depositing nano wire film first, then fusion solution can be added in nano wire film, this can be carried
For patterning as further discussed below, the relative quantity of reactant is adjusted, different solvents system is used for different solutions,
It avoid the need for using in the fusion solution of mixed solution immediately before use and etch sour and other current potentials selections.Processing can be with
At low temperature (such as at room temperature) carry out.The processing method as described herein fused using nano wire can be effectively adapted
To form various device assemblies, such as tactile sensor as described below.
Any rational coating method, such as dip-coating, spraying, edge of a knife coating, rod painting, the coating of plum ear bar can be used
The coating of (Meyer-rod coating), slit-type squash type, notch board coating, spin coating etc..With dispersion liquid formed coating it
Afterwards, can be with drying nano gauze network to remove liquid.Dry metal nanowire film can then be handled to realize that nano wire melts
Close.
As described in following instance, processing method specifically described herein causes the fusion of metal nanometer line.It is believed that this is molten
Conjunction helps to strengthen observed electric conductivity and contributes to the achievable improved transparency under reduced levels resistance.It is believed that
Fusion occurs at the proximity contact of adjacent nano wire during processing.Therefore, fusion can be related to end-to-end fusion, side wall pair
Sidewall fusion and end are to sidewall fusion.Degree of fusion can be relevant with treatment conditions.As further discussed below, it is believed that compared with weakness
The reason time contributes to good fusion and degraded without nanometer line network.
For a variety of solution methods, the first solution is generally deposited to form metal nanowire film.Metal nanowire film is being entered
One step processing before can through dry or can be without drying.Then fusion solution can be added into metal nanowire film to enter
Row fusion.In certain embodiments, it is believed that fusion occurs during fusion solution is dried, during this period drying process increase metal
Ion concentration.As material is dried, it is believed that liquid can be pooled to the region that chemical potential is relatively low in the film between nanostructured.
Film can be dried for example with heat gun, baking oven, heating lamp etc..In general, film can be heated to during drying
About 50 DEG C to about 100 DEG C of temperature.After the drying, can for example with alcohol or other solvents or solvent blends (such as ethanol or
Isopropanol) film is washed one or more times to remove Excess solid so as to reduce turbidity.
For the processing of single solution, single coating step is deposited together metal nanometer line and fusion agent.In general,
Single solution can before the use usually no more than about 24 hours when mix, be no more than before the use in certain embodiments
Mixed when mixing and be no more than about 5 hours before the use in other embodiments at about 10 hours.In certain embodiments,
A part of the solution as coating process can be merged before it will be coated with.After film is formed, film can be dried, and
It is believed that fusion occurs during drying.It can be dried as described in paragraph in the case of distinctly fusion solution.
For example fusion network can be washed with alcohol or other solvents or solvent blends remove Excess solid one or more times.
Conductive film structure and property
The fusion metal that conducting film specifically described herein generally comprises substrate and is deposited on substrate surface or part thereof is received
Nanowire network.Optional polymer coating can be placed on above metal nanometer line network fuses nanometer to protect and stablize
Gauze network.The parameter of metal nanometer line can be adjusted to obtain the required property of fusion network.For example, higher load amount
Nano wire can be produced compared with low resistance, but transparency may reduce with higher nanowire supported amount.Via balance these parameters,
The electric conductivity and optical clarity of level needed for can obtaining.Observed by such as in scanning electron micrograph, improved network
In nano wire be fused.It is believed that the fusion of nano wire produces improved electric conductivity, while maintain the optical clear of higher level
Degree.Stable conductive structure will be provided within the reasonable life-span of corresponding product with the network for possessing fusion nano wire.
In general, suitable substrate can be selected as needed based on application-specific.Substrate surface can include example
Such as polymer, glass, inorganic semiconductor material, without electromechanical dielectric material, polymer glass laminates, its compound.Properly
Polymer include such as PET (PET), PEN (PEN), polyacrylate, poly-
(methyl methacrylate), polyolefin, polyvinyl chloride, fluoropolymer, polyamide, polyimides, polysulfones, polysiloxanes, polyethers
Ether ketone, polynorbornene, polyester, polystyrene, polyurethanes, polyvinyl alcohol, polyvinyl acetate, acrylic nitrile-butadiene two
Alkene-styrol copolymer, makrolon, its copolymer or its admixture etc..In addition, material can have positioned at fusion metal
Polymer coatings on nanometer line network, and cover with paint, lacquer, colour wash, etc. one polymer and can include for the polymer listed by above substrate.
Furthermore, it is possible on conducting film and substrate or between add other layers with reduce that reflection loss and improving stacks it is overall thoroughly
Penetrate rate.
After metal nanometer line is fused into network, individual nanowires are there would not be, but for forming network
The physical property of nano wire is reflected directly in the property of fusion nanostructured network.As described above, it is delivered to receiving on substrate
The amount of rice noodles can be related to the balance of each factor so as to obtain the desired amount of transparency and electric conductivity.Although the thickness of nanometer line network
Degree can be assessed using scanning electron microscopy in principle, but the network is probably relatively brittle, and this may make measurement
Complicate.In general, fuse metal nanometer line network average thickness will no more than about 5 microns, in a further embodiment
No more than about 2 microns and be about 25nm to about 500nm in other embodiments.However, fusion nanometer line network is typically to have
There is the structure of the opposing open of the notable surface texturisation of submicron scale, and have indirect method only to be generally used for estimating thickness.
The load capacity level of nano wire can provide the suitable parameters for the network that can be easy to assess, and load magnitude offer has with thickness
The alternative parameter closed.Therefore, as used herein, substrate of the load capacity level of the nano wire on substrate for square centimeter
Exist with microgram or milligram nano wire.In general, nanometer line network can have about 0.01 milli gram/m (mg/m2) arrive
About 200mg/m2, about 0.025mg/m in a further embodiment2To about 150mg/m2And in other embodiments about
0.05mg/m2To about 100mg/m2Load capacity.Those of ordinary skill in the art are it will be recognized that more than in clear and definite scope
Thickness and load capacity other scopes covered in and in this disclosure.
Resistance can be expressed as sheet resistance, and it is reported with the unit of ohms per square (Ω/ or ohm-sq), from
And described value and body resistance value are distinguished according to the parameter relevant with measuring method.The sheet resistance of film is usually using 4 points
Probe measurement or equivalent method measure.In the following example, film sheet resistance is measured using four-point probe, or by using
The agent of rapid draing silver paste is made one square to measure.The sheet resistance of fusion metal nanometer line network can be no more than about 200 Europe
Nurse/square, in a further embodiment no more than about 100 ohm-sqs and in other embodiments be no more than about 60 ohm/
Square.Those of ordinary skill in the art are it will be recognized that other scopes of the sheet resistance more than in clear and definite scope are contained
Including lid and in this disclosure.In general, sheet resistance can be reduced by increasing the load capacity of nano wire,
But increased load capacity as further discussed below, is may not be needed from the point of view of other viewpoints, and for improving sheet resistance
For load capacity not as realizing that good fusion is important.
For the application as nesa coating, fusion metal nanometer line network needs to maintain good optical transparency.One
As for, optical clarity and load capacity inversely related, but the processing of network may also significantly affect transparency.Optical clarity
It can be assessed with respect to the light of substrate transmission.For example, the transparency of conducting film specifically described herein can lead to
Cross and measured using UV- visible spectrophotometers and measurement by conducting film and the total transmittance of support substrate.Transmissivity
It is transmitted intensity (I) and incident intensity (Io) ratio.Pass through the transmissivity (T of filmFilm) can be by will be measured total
Transmissivity (T) divided by the transmissivity (T for passing through support substrateSubstrate) estimate.(T=I/IoAnd T/TSubstrate=(I/Io)/(ISubstrate/
Io)=I/ISubstrate=TFilm) therefore, the total transmittance reported makes to be removed from described value by the transmissivity of substrate.It is although logical
Often need that there is good optical transparency in visible spectrum, but for convenience, light transmission can be under 550nm wavelength lights
Report.Besides or furthermore, transmissivity can be reported to the total transmittance of 400nm to 700nm wavelength lights, and the result is reported
In following instance.Generally, for fusion metal nanowire film, 550nm transmissivities and 400nm to 700nm total transmission
The measurement of rate (or for convenience only " total transmittance ") is not qualitatively different, but in some embodiments of nesa coating
In, total transmittance can be higher 1%-2% than 550nm transmissivity.In certain embodiments, the film formed by fusion network has extremely
Lack 80%, in a further embodiment at least about 85% and in other embodiments at least about 90% total transmittance.It is transparent
The transparency of film can use standard ASTM D1003 (" the transparent modelings being incorporated herein by reference in polymer substrate
The turbidity of material and standard method of test (the Standard Test Method for Haze and Luminous of transmittance
Transmittance of Transparent Plastics) ") assess.As described above, possible especially needed good optical is saturating
Lightness and more low-resistance correlation.In some embodiments that sheet resistance is 20 ohm-sqs to about 150 ohm-sqs,
The total transmittance of film can be at least about 86%, be in a further embodiment at least about 88% and be in other embodiments
About 89% to about 95%.In one embodiment, film can have the no more than about sheet resistance of 75 ohm-sqs and at least about
85% total transmittance.In another embodiment, film can have the no more than about sheet resistance of 175 ohm-sqs and at least
About 90% total transmittance.Those of ordinary skill in the art are it will be recognized that light transmission more than in clear and definite scope
In other scopes are covered in and in this disclosure.
Sintering metal network can also have compared with low turbidity and compared with high visible light transmissivity, while have required relatively low thin
Layer resistance.Turbidity can be measured based on above-mentioned ASTM D1003 using nephelometer, and can remove the turbid of substrate
Degree is contributed to provide the turbidity value of nesa coating.In certain embodiments, sintering the turbidity value of network film can be no more than about
0.5%th, 0.45% and in other embodiments no more than about 0.4% is no more than about in a further embodiment.Art
Skilled artisan will realize that, in other scopes of the turbidity more than in clear and definite scope are covered in and in originally taking off
Show in content.
Patterning
Processing method specifically described herein can be used for effective patterned film, have required optical lens so as to be formed on film
The pattern of the conductive region of lightness and less conductive region.Exactly, due to being chemically sintered/fusion process,
Therefore controlled transmission of the agglutinant to the selected portion of metal nanowire film can be formed at the film part contacted with agglutinant
Sintering metal network, while the metal nanowire film of remainder keeps un-sintered.Certainly, the control of agglutinant transmission is for treating
Effective for not necessarily must be perfect for the patterning suitably applied.The pattern of selectivity transmission based on fusion agent along substrate
Change can be effectively formed under white light eyes in fact invisible pattern.Metal is fused based on effective patterning with selectivity to receive
Discovery based on rice noodles film, similar pattern structure can use by radiate the metal nanometer line that is guided in pattern based on
The fusion of radiation and formed.Although the patterning based on the pattern fusion nano wire selected by has many required aspects,
The patterning or subraction patterning carried out via material is removed can be carried out.
Generally instructed along the specific pattern of the fusion conductive network of substrate surface by required product.Certainly, for some
For product, whole surface is electrically conductive, and for these applications, generally without patterning.For being related to patterning
Embodiment, the ratio on the surface comprising conductive sintering network may be usually based on selected design to be selected.In some implementations
In example, fusion network accounts for about 1% to about the 99% of surface, accounts for about 5% to about 85% in other embodiments and in other realities
Apply and about 10% to about the 70% of substrate surface is accounted in example.Those of ordinary skill in the art it will be recognized that more than clear and definite model
In other scopes of surface coverage in enclosing are covered in and in this disclosure.Can along the fusion network on surface
With conductive pattern of the formation as shown in Figure 1A with single-pathway 21 or as shown in fig. 1b with multiple conductive paths 23,25
With 27 conductive pattern.As shown in fig. 1b, fusion area forms three different conductive regions 23,25 and 27.It is although single
The conductive region of connection and the conductive region of three independent connection have been showed in figure, it should be understood that can be formed as needed
With two, four or more than 4 conductive independence conductive paths or the pattern in region.Similarly, can select as needed
The shape in particular conductivity region.
Difference between the fusion network area on surface and the electric conductivity of incomplete fusion nano wire region can provide required work(
Can property.In general, as described in example, the electric conductivity change between fusion area and incomplete fusion region may be very big, but
More little contrast still can be effective.In general, the sheet resistance in incomplete fusion metal nanometer line region is fusion metalolic network
At least about 10 times of sheet resistance, at least about 100 times in other embodiments, at least about 1000 times in other embodiments,
And be in other embodiments fuse at least about 1,000,000 times of sheet resistance of metalolic network or bigger multiple (such as
Up at least 109Ohm-sq is bigger).Can by silver paste agent is coated onto on sample surfaces first with define one square come
High resistance measurement is carried out on such as incomplete fusion network or naked polymer substrate.Sample can then anneal 20 at about 120 DEG C
Minute so as to by silver-colored paste curing and drying.Crocodile clip (alligator clip) is connected to silver paste agent, and wire can
To be connected to suitable high resistance measurement apparatus, such as the low electricity of Alpha laboratory (AlphaLabs) high resistance under electrical shielding
Lead meter.High resistance measured value is recorded and is described in following instance.Instrument can measure at most 1999 gigohm nurses.Affiliated neck
Domain skilled artisan will realize that, in other scopes more than in clear and definite scope are covered in and in this announcement
In appearance.Can be with approximately the same on fusion metalolic network and incomplete fusion metal nanowire film to the optical clarity of visible ray.Cause
This, film can be uniform on the surface of a substrate in eyes in white light, so that patterning looks invisible.It is invisible
Pattern can be some application needed for.
The fusion of metal nanowire film and the patterning in incomplete fusion region can be driven by fusing the selectivity transmission of agent
It is dynamic.In general, metal nanowire film can be delivered to surface first.Metal nanowire film can be passed on surface or
Some is suitably partly upper relatively uniform.Certainly, a part of surface can keep not being coated with by nano wire film completely, and refer to
Patterning refers to have the part on the surface of nano wire film, the i.e. fusion of film and incomplete fusion part.Using molten based on halide
During ' 221 of the patterning reference described above of mixture are applied.
If the liquid solution comprising fusion agent is administered to metal nanowire film, then fusion solution can be delivered to
The selected portion of film is to be fused.Although the shade of excellent sealing can be used for the selected portion for preventing liquid fusion agent and film
Contact, but ink jet printing, silk-screen printing or other appropriate printing processes may be needed to use by institute of the liquid agglutinant along film
Need printed portions.The property of liquid fusion agent, which can be conditioned, is suitable for specific printing process.A small amount of liquid fusion can be transmitted
Agent is to provide appropriate fusion.Liquid and/or printing process can be controlled to limit the distribution of fusion liquid or make distribution controlled
To provide the fusion above selected areas.In addition, conventional photolithographic method (such as using photoresist) can be used for manufacture shade with
Define the region that nano wire contacts with fusing solution.
The heat fused or sintering of nano silver wire may be highly difficult, because nano wire is more than the stabilization of polymer substrate in temperature
Possibly it can not be sintered before warm-natured degree.It can be used for solving this difficulty in the following manner using radiation:Direct radiation onto silver
In nano wire, while polymer substrate can be with relative transparent so that the thermic load on substrate is reduced for radiation.Nano silver wire
The report of laser ablation is reported in ripple cevine (Pothoven), " laser patterning (the Laser Patterning of nano silver wire
Of Silver Nanowires) ", presentation of information magazine (Information Display Magazine), the 28th (9) volume,
In September, 2012, electronic document, it is incorporated herein by reference.Although the laser ablation of nano wire can cause to substrate
Relatively appropriate damage, but the fusion of nano wire can be carried out under significantly lower dose of radiation, the significantly lower spoke
Penetrate dosage and radiation damage to substrate will be further reduced for many substrates.Although ultraviolet light, visible ray and/or infrared
Light can be used for fuse metal nanometer line, but infrared ray can due to the less damage generally to substrate but it is required.One system
Laser (such as PRK or YAG laser) of the row with selected wavelength can be used for the radiation fusion of patterned film, and
Laser control system can be used for selected location scanning light beam.Guiding the commercial system of the laser of scanning includes such as scanning in fact
Test room (ScanLabs) scanner.Furthermore, it is possible to by high intensity infrared lamp (such as flash lamp based on inert gas) aligning film
To be sintered, and shade can be used for defining pattern.Fast speed heat is carried out on semiconductor devices using high intensity heating lamp
It is entitled " using rapid thermal annealing that annealing is described in the Hanna Maria Seppala (Seppala) being incorporated herein by reference et al.
Manufacture semiconductor device protruded electrode (Process for Manufacturing a Semiconductor Device Bump
Electrode Using a Rapid Thermal Anneal) " United States Patent (USP) 5,665,639 in, and described device can
To be adapted for use in metal nanometer line fusion.
For subraction patterning, metal removes from the region being identified with high electrical resistance.The removal of metal can
Effectively to carry out fusing into nano wire on the surface after fusion network, but can fuse in certain embodiments
The removal of metal nanometer line is carried out before or after patterning fusion.If received before fusion for patterning into row metal
The removal of rice noodles, then fusion agent can be then applied in above whole patterned surfaces, because high resistance area can be substantive
It is upper to be free of metal nanometer line.From need high electrical resistance region remove metal can via etching or carry out under the radiation.In order to
Wet chemical etch is carried out, patterning shade can be applied using such as conventional photolithographic method and photoresist.For removing metal
The suitable wet etchant of nano wire can include such as 8M nitric acid or 3M copper chlorides/hydrochloric acid.In the case of positivity photoresist,
The photoresist applied is exposed through and developed with region of the exposure for etching, and after the etching, removes photoresist.For
The removal based on radiation of metal, in addition to removing metal rather than fusion metal except transmitting appropriate higher dose, radiation
It can be similarly used for fusing metal nanometer line under radiation as described above.Exactly, infrared laser or infrared heating
Lamp can degrading with the commonly provided metal, and it is smaller relative to some to degrade damage of the method to substrate.Scanning laser light beam
Or screening of radiation can be used for defining patterning under the radiation.It is about 10 that subraction patterning, which can produce sheet resistance,7Ohm/
Square to 109The region of ohm-sq or bigger ohm-sq.
Effective patterning of conductive transparent film can be very effective for some displays and/or tactile sensor application
's.Exactly, tactile sensor can ideally the pattern with conductive region to provide the corresponding of tactile sensor
Pattern, and transparency provides visualization of the display etc. under pattern as follows.
Tactile sensor
The common trait of tactile sensor is typically in its natural state (i.e. without contacting or otherwise outside
When portion contacts) exist in two transparent conductive electrode structures for being spaced apart collocation form.For according to capacitance operation sensor,
Dielectric layer is usually located between two electrode structures.Referring to Fig. 2A, the tactile sensor 101 based on electric capacity includes display module
103rd, optional base substrate 105, the first transparent conductive electrode structure 107, dielectric layer 109 (such as polymer or sheet glass
Material), the second transparent conductive electrode structure 111, optional top substrate 113 and measure with sensor contact correlation electric capacity change
The measuring circuit 115 of change.Referring to Fig. 2 B, the touch sensor 131 based on resistance includes display module 133, optional lower section
Substrate 135, the first transparent conductive electrode structure 137, the second transparent conductive electrode structure 139, support electrode structure are in its nature
The supporting construction 141 of configuration spaced apart in configuration, 143, upper substrate 145 and resistance measuring circuit 147.
Display module 103,133 can be LED-based display, LCD display or other required display modules.Substrate
105th, 113,135,145 can be transparent polymer sheet material or other clear sheets.Supporting construction can be formed by electric dielectric material,
And sensor construction can include other supporters to provide required stabilising arrangement.Measuring circuit 115 and 147 is in affiliated neck
It is known in domain, and refers to some particular sensor embodiments in the situation of patterning below.Transparent conductive electrode
107th, 111,137 and 139 sintering metal network can be efficiently used formed, but in certain embodiments, sintered metal net
Network forms some electrode structures, and other electrode structures in device can include such as tin indium oxide, Al-Doped ZnO etc.
Material.Fusing metalolic network can be as described herein and by effective pattern, and it can desirably be used for
Patterned film is incorporated in one or more electrode structures to form sensor so that the multiple electrodes in transparent conducting structures can be used
In the offer positional information related to contact process.Patterning tactile sensor is formed using patterned transparent conductive electrode
Be described in it is following in:Such as palace sheet (Miyamoto) et al. entitled " tactile sensor, the display with tactile sensor
Device and method (Touch Sensor, Display With Touch Sensor, the and Method for generating position data
For Generating Position Data) " United States Patent (USP) 8,031,180 and sakata (Sakata) et al. it is entitled " narrow
The touch tablet of frame, the method for manufacturing the tablet and for the conductive sheet (Narrow in the touch tablet of narrow frame
Frame Touch Input Sheet,Manufacturing Method of Same,and Conductive Sheet
Used in Narrow Frame Touch Input Sheet) " U.S. Patent Application Publication 2012/0073947, it is described
Application is incorporated herein by reference.
Example
There to be different size of commercially available nano silver wire to be used for following instance.The property of nano silver wire have 30nm with
The average length of average diameter and 10-15 microns between 40nm.Nano silver wire (AgNW) film is formed using following procedure.By city
Nano silver wire (AgNW) is sold to disperse in a solvent to form AgNW dispersion liquids.AgNW dispersion liquids are in alcoholic solvent generally in 0.1 weight
Measure in the range of % to 1.0 weight %.Dispersion liquid is then deposited on glass or poly terephthalic acid using spraying or pull rod method
AgNW films are used as on second diester (PET) surface.Then AgNW films are briefly exposed to selectivity fusion agent to form fusion gold
Belong to nanostructured network.Also a kind of ink or the two kinds of ink systems for being blended directly in AgNW in ink solution with fusing agent are developed
System.
The total transmittance (TT) and turbidity of AgNW membrane samples are using nephelometer in the case where film is located in polymer substrate
Measurement.Turbidity from independent PET substrate is about 0.4%., can be from the survey in order to adjust the turbidity measurement of following sample
Value subtracts 0.4% value to obtain the approximate turbidity measurement of independent nesa coating.Instrument is designed to be based on to quote
The standards of ASTM D 1003 (" turbidity of transparent plastic and the standard method of test of transmittance ") that are incorporated herein of mode comment
Estimate optical property.The total transmittance and turbidity of these films include PET substrate, and it, which has, respectively about 93.3% and 0.3% arrives
0.4% basic total transmittance and turbidity.Unless otherwise noted, otherwise sheet resistance is measured using 4 point probe methods.In following reality
In example, several different solution agglutinants are presented.(especially) for providing film sinters front and rear transparent conductor property and sheet resistance.
The network of nano wire can be made up of silver and some polymer that may act as ink dispersant or adhesive.Representative high resistance is surveyed
Amount is carried out in the incomplete fusion metal nanowire film formed for these examples.In order to measure, one square of silver paste agent is applied
To define one square on to sample surfaces, it then anneals 20 minutes to solidify and dry silver paste agent at about 120 DEG C.By crocodile
Fish folder is connected to silver paste agent, and wire may connect to suitable high resistance measurement apparatus.Three Represents measured value is>1000
Lucky ohm-sq (1012Ohm-sq), the 1000 gigohm nurses/lucky ohm-sq (10 of quadratic sum 10011Ohm-sq).
Example 1 has the fusion composition in different silver-colored sources, acid and solvent
This example tests combination fusion ability as fusion agent of the different silver-colored sources from several acid in different alcohol.It is used
It is all acid under about 0.01-1.0 μ L/mL (0.001-1.0 volume %, i.e. volume/volume or 0.00157M to 0.157M),
And all silver salt used are under 1.0mg/mL.Fusion agent 1-10 composition is listed in the table below in 2.Fusion agent is administered to
AgNWs films, and compare in table 2 property of the film before and after fusion agent is applied, wherein film 4,6 boxes 7 are not include acid
Or the control of silver salt.AgNW inks are formed in isopropanol or isobutanol or other solvents with 0.01-0.5 weight %.Ink connects
Using plum ear bar or blade coating to be coated with.The film heat gun or several seconds of infrared lamp rapid draing are to flash off solvent.
Fusion solution is then deposited using spraying or blade coating.After coating, film uses heat gun or the fast rapid-curing cutback of infrared lamp
It is dry to dry solvent.Equivalent silver nanowire film is used for test case 1-9 fusion solution.
Measure film 1-7 resistance and draw result in figure 3.As shown in Figure 3, composition 1 seems not cause molten
Close, because the resistance of film is still higher.The film handled with composition 2,3,4,5,6 and 7 shows significantly reduced resistance, indicates
Fusion or sintering occur in these membrane samples.Fig. 3 a are the surfaces for the film for representing membrane sample 5 under different amplification
The composite diagram of the SEM image of collection and fusion or the sintering for showing nano wire.Fuse composition 7 exactly only in ethanol
Containing 1.0 μ L/mL nitric acid and without additional silver salt, and such as it can successfully sinter nanometer according to indicated by reducing resistance
Line.Exactly, before sintering, the resistance of film 7 is more than 20,000 ohm-sq.After the sintering, the resistance of film 7 is about
150 ohm-sqs.Because sample 7 only has nano silver wire as metal source, so example displaying oxidizing acid (such as nitric acid)
Metal can be made mobile and lure that adjacent nano wire fuses into fusion network into.
Table 2
Ethanol of the example 2 containing nitric acid is as fusion solution
Caking power of the ethanol containing nitric acid as fusion agent is further tested in this example.Exactly, containing about
Solution of the 0.01-1.0 μ L/mL nitric acid in EtOH is cast by blade coating to drying on AgNW films, and the dry AgNW films lead to
Crossing will form on AgNW dispersion liquids blade coating to substrate.Form four repetition membrane samples.Measurement apply sinter solution before and
Caudacoria resistance, and result is drawn in Fig. 4.Resistance variations may be attributed to film or corresponding dispersion liquid and/or coated articles
The change of matter.As shown in Figure 4, the initial resistance of film is up to 20,000 ohm-sq, and accordingly sinters the film exhibition of solution processing
Show resistance only between 80-140 ohm-sqs and>90 total transmittances (TT) (including PET substrate) and low turbidity.Due to PET
The TT of substrate is about 93%, therefore the TT of conducting film is correspondingly higher.It should be noted that the initial resistance of these samples before treatment
May be much larger than recorded 20,000 ohm-sq, but exceed the detection range of hand-held four-point probe used.Therefore observe
Substantially reduced to the high TT of holding and low turbidity, the resistance of film.
Example 3 is containing the ethanol of silver nitrate and nitric acid as fusion solution
Caking power of the ethanol containing silver nitrate and nitric acid as fusion agent is tested in this example.AgNW films 1-6 be by
0.01-0.5 weight % solution-casts.0.1mg/mL AgNO will be contained3With 1.6 μ L/mL HNO3Fusion solution in EtOH is applied
Use in film.Resistance, total transmittance and the turbidity (including PET) of film are measured, and result is listed in the table below in 3.Such as institute in table 3
Show, the initial resistance of AgNW films 1-6 network is shown as being higher than 20,000 ohm-sq.After with fusion solution processing,
AgNW films 1-6 displaying between 75-203 ohm-sqs resistance and>90 total transmittances (TT) (including PET substrate) and
Low turbidity.Because the TT of PET substrate is about 93%, therefore the TT of conducting film is correspondingly higher.Therefore observe with the high TT of holding
And low turbidity, the resistance of film substantially reduce.Relative to without AgNO3In the case of the corresponding membrane sample (not shown) that is formed, table 3
The result of middle presentation is generally more consistent.Fig. 4 a are the composite diagrams for representing the SEM image of the film different piece of film 1 and 2 in table 3.Institute
State SEM image displaying AgNW sintering.
Table 3
(ohm-sq) before | (ohm-sq) afterwards | Final TT (%) | Turbidity % | |
1 | >20,000 | 203 | 91.4 | 1.11 |
2 | >20,000 | 203 | 92.1 | 0.98 |
3 | >20,000 | 75 | >90.0 | 1.51 |
4 | >20,000 | 174 | >90.0 | 1.24 |
5 | >20,000 | 100 | >90.0 | 1.11 |
6 | >20,000 | 111 | 92.9 | 0.83 |
Example 4 has the fusion composition in different silver-colored sources in ethanol
This example tests different silver-colored sources and the fusion ability of the combination of nitric acid or perchloric acid in ethanol.Own in EtOH
Silver-colored source is 0.1mg/mL and all acid are 1.6 μ L/mL.Silver-colored source used includes AgF, Ag- acetate, Ag- trifluoros
Methane sulfonates (AgTMS), Ag- hyptafluorobutyric acids salt (AgFHB) and Ag- hexafluoro antimonates (AgHFA).Measure the fusion used of film
Reagent, resistance, total transmittance and turbidity (including PET), and result is listed in the table below in 4 and 5.As shown in table 4 and 5, AgNW
The initial resistance of film is shown as being higher than 20,000 ohm-sqs.After with fusion agent processing, the displaying of AgNW films has in 50-
Resistance between 200 ohm-sqs, wherein exception is through AgBF4The film of processing, its resistance are 500 ohm-sqs.Handling
The total transmittance (TT) of caudacoria seem to be higher than 91, and turbidity is relatively low, wherein exception is through perchloric acid-AgHClO4Processing
Film, its turbidity are 11.4.Therefore observe substantially reduces with the high TT of holding and low turbidity, the resistance of most of film.
Table 4
Silver-colored source | Acid | Before ohm-sq | After ohm-sq | Final TT | Final turbidity |
AgF | HNO3 | >20,000 | 110 | 91.7 | 1.14 |
Ag- acetates | HNO3 | >20,000 | 150 | 91.5 | 1.33 |
Ag-TMS | HNO3 | >20,000 | 75 | 91.8 | 0.93 |
AgFHB | HNO3 | >20,000 | 90 | 91.5 | 0.96 |
AgHFA | HNO3 | >20,000 | 110 | 91.1 | 1.07 |
AgBF4 | HNO3 | >20,000 | 500 | 91.7 | 1.5 |
AgHClO4 | HClO4 | >20,000 | 200 | 92.5 | 11.4 |
Table 5
Silver-colored source | Acid | Before ohm-sq | After ohm-sq | Final TT | Final turbidity |
AgHFB | HNO3 | >20,000 | 103 | 92.4 | 0.88 |
AgHFB | HNO3 | >20,000 | 108 | 92.5 | 1.05 |
AgHFB | HNO3 | >20,000 | 50 | 92.1 | 1.24 |
AgTMS | HNO3 | >20,000 | 95 | 92.0 | 1.03 |
AgTMS | HNO3 | >20,000 | 100 | 92.2 | 0.91 |
AgTMS | HNO3 | >20,000 | 103 | 92.2 | 0.92 |
Comparison of ethanol of the example 5 containing silver nitrate and silver fluoride as fusion agent
This example compares silver nitrate and silver fluoride when being combined in from nitric acid in ethanol as fusion agent in different AgNW films
On fusion ability.AgNW films are by 0.01-0.5 weight % solution-casts.It is used fusion agent be AgF containing 0.1mg/mL or
AgNO3With 1.6 μ L/mL HNO3EtOH.Four repetition membrane samples are made using AgF as fusion agent, and use AgNO3Make
Four repeat samples are made for fusion agent.Measure in each membrane sample the corresponding resistor, total of sintering reagent used and film
Transmissivity and turbidity (including PET), and result is listed in the table below in 6.Difference between similar membrane sample may be attributed to coating
Or the change of the quality of AgNW dispersion liquids before coating.As shown in table 6, the initial resistance of AgNW films is shown as being higher than 20,000
Ohm-sq.After with fusion agent processing, the displaying of AgNW films, which has, is less than 150 ohm-sqs (for what is handled through AgF
Film) and less than 100 ohm-sqs (for through AgNO3The film of processing) resistance.The total transmittance (TT) of processing caudacoria seems high
In 91% (for the film handled through AgF) and higher than 92% (for through AgNO3The film of processing), have and be less than 1.4% (for warp
AgF processing film) and less than 1.02% (through AgNO3The film of processing) relatively low turbidity.Although therefore in silver nitrate and silver fluoride
Observe that it was observed that resistance substantially reduces in film, but silver nitrate seems that generation has with high TT and low turbidity is kept in both
Compared with low resistance, higher TT and the film compared with low turbidity.
Table 6
Silver-colored source | Acid | Before ohm-sq | After ohm-sq | Final TT | Final turbidity |
AgF | HNO3 | >20,000 | <150 | 91.2 | 1.35 |
AgF | HNO3 | >20,000 | <150 | 91.7 | 1.16 |
AgF | HNO3 | >20,000 | <150 | 91.4 | 1.26 |
AgF | HNO3 | >20,000 | <150 | 91.5 | 1.37 |
AgNO3 | HNO3 | >20,000 | <100 | 92.5 | 1.00 |
AgNO3 | HNO3 | >20,000 | <100 | 92.5 | 1.02 |
AgNO3 | HNO3 | >20,000 | <100 | 92.5 | 0.88 |
AgNO3 | HNO3 | >20,000 | <100 | 92.5 | 0.99 |
The palladium of example 6 sinters solution
The displaying of this example fuses the ability of metal nanometer line with the metallic element different from the metal of nano wire.Therefore, palladium
Solution is sintered in this example as fusion agent test.
0.0005-0.005 molar concentrations palladium (Pd) salt is made in ethanol.Add 1.0 μ L/mL HNO3.Measure each
The corresponding resistor and total transmittance (including PET) of fusion reagent used and film in membrane sample, and result is listed in the table below 7
In.Because the TT of PET substrate is about 93%, therefore the TT of conducting film is correspondingly higher.As shown in table 7, the initial electricity of AgNW films
Resistance is shown as being higher than 20,000 ohm-sqs.After with fusion agent processing, although the resistance of film has been substantially reduced, its
Still it is higher compared with after being handled using other fusion agent.Only through Pd (NO3)2Film displaying with nitric acid treatment, which has, to be less than
The resistance of 150 ohm-sqs.Use Pd (NO3)2With nitric acid as fusion agent as further visited described in the example 6 below
Rope.
Table 7
Palladium source | Acid | Before ohm-sq | After ohm-sq | Final TT |
K2PdCl4 | Nothing | >20,000 | 1,130 | 86.8 |
K2PdCl4 | HNO3 | >20,000 | 880 | 85.9 |
Pd(NO3)2 | Nothing | >20,000 | 235 | 90.2 |
Pd(NO3)2 | HNO3 | >20,000 | 140 | 91.1 |
The other metal sintering solution of example 7
Metal source (such as palladium and copper) in addition to silver is used as to fusion agent in this example.It is made in ethanol
0.00005-0.005 molar concentrations palladium (Pd) or mantoquita.Add 1.6 μ L/mL HNO3.For fusing solution Pd2 and Pd4, in addition
0.1mg/mL AgF are added to form sintering solution.Measure in each film the corresponding resistor, total of fusion agent used and film
Transmissivity and turbidity (including PET), and result is listed in the table below in 8.The initial resistance of AgNW films higher than 20,000 ohm/it is flat
Side.Resistance after processing is the average value obtained from three data points.As shown in table 8, after with fusion agent processing, AgNW
Film displaying is with the resistance between 32 ohm-sqs and 117 ohm-sqs.The total transmittance (TT) of processing caudacoria seems
Between 88 and 91 (including PET substrate).Using Wei Yike companies (Veeco) AFM instruments, and 10 × 10 μm scan through capture,
Carried out and be showed in Fig. 5 with the sample P d3 AgNW networks formed, indicate the clear growth of nanometer line network.Fig. 5 a are generations
The composite diagram for the SEM image that the surface of sample P d1 film gathers under different amplification and nano wire is shown in table table 8
Fusion or sintering.
Table 8
Sinter solution | Resistance (ohm-sq) | TT% | |
Pd1 | 5×10-4Pd(NO3)2+1.6μl/ml HNO3 | 41 | 89.7 |
Pd2* | 5×10-4Pd(NO3)2+1.6μl/ml HNO3+AgF | 32 | 88.7 |
Pd3 | 5×10-5Pd(NO3)2+1.6μl/ml HNO3 | 117 | 90.6 |
Pd4* | 5×10-5Pd(NO3)2+1.6μl/ml HNO3+AgF | 33 | 90.3 |
Cu1 | 5×10-3Cu(NO3)2+1.6μl/ml HNO3 | 65 | 88.7 |
Example 8 compares copper and silver salt
Copper is used as metal salt in sintering solution and in this example compared with silver salt.Measure in each membrane sample
Fusion reagent used and corresponding resistor, total transmittance and the turbidity (including PET) of film, and result is listed in the table below in 9.
The initial resistance of AgNW films is higher than 20,000 ohm-sqs.Resistance after processing is the average value obtained from three data points.Consumption
When about 10 minutes with using comprising ethanol copper solution formed sintering network.
Table 9
Metal used | Sinter solution | Ohm-sq | TT% | Turbidity | |
Cu1a | Copper | 5×10-4Molar concentration Cu (NO3)2+1.6μl/ml HNO3 | 78 | 90.1 | 1.63 |
Control | Silver | 0.1mg/ml AgNO3, 1.6 μ l/ml HNO3 | 63 | 90.8 | 1.58 |
Copper solution is shown and the solution (AgNO based on silver3, HNO3System) similar performance.Compared with earlier experiments for
Cu preferable turbidity and optical characteristics is by the way that copper concentration used is reduced into 1/10th to obtain.Carry out molten with dilute cupric
Liquid (5 × 10-4Cu(NO3)2) formed AgNW networks AFM and be showed in Fig. 6, indicate the clear life of nanometer line network
It is long.
Example 9 is used to fuse the Jin Heqian in solution
Gold and lead are used as metal salt in solution is fused in this example.Measure fusion examination used in each membrane sample
The corresponding resistor of agent and film, total transmittance and turbidity (including PET), and result is listed in the table below in 10.AgNW films it is initial
Resistance is higher than 20,000 ohm-sqs.Resistance after processing is the average value obtained from three data points.Fusion containing gold is molten
Liquid seems AgNW being lifted out substrate PET.After with the solution processing of fusion containing gold, the resistance of film is not obtained.This is it is believed that attribution
In gained film bad adhesion strength and be not based on gold fusion solution intrinsic property.Lead processing caudacoria resistance seemingly
It is of a relatively high, about 316 ohm-sqs.The film handled through lead seems there is good TT and compared with low turbidity.
Table 10
A kind of 10 ink solution of example fuses
This experimental exploring will fuse agent and AgNW inks mix and are coated on such as PET substrate in the solution
Method on substrate.Use several solvents based on organic matter and alcohol.A kind of ink typically refers to fusion agent and has been integrated in ink
In system.Reducing agent used is typically solvent in these embodiments, or can be added to reducing agent in fusion solution.
It has been provided for the general introduction of the various compounds and mechanism of fusion.Many volume/concentration ratios are screened, in some cases will be small
Volume fusion solution (FS) is added in AgNW inks;In other cases AgNW is directly appended to fuse in solution (FS).
Explore three kinds of sintering solution (FS):CT1)AgF(0.1mg/mL)+HNO3(1.6μL/mL);CT2)AgNO3(0.1mg/mL)+HNO3
(1.6μL/mL);And CT3) separate out AgF (1.0mg/mL EtOH solution, its through body lotion be ultrasonically treated 30 minutes and then via
0.45 μm or 0.2 μm of PTFE filters filtering).Because HNO3AgNW can be etched, it is therefore important that just coating process it
Preceding obtained solution CT1 and CT2.The AgNW that concentration is 0.01 weight % to 0.5 weight % is prepared in ethanol or isopropanol to disperse
Liquid.Fusion solution is also prepared with prescribed concentration in ethanol.Isopropanol (IPA) is used as retarder thinner.AgNW/IPA/FS is with milli
The ratio for rising meter is illustrated in table 10 below -12.The resistance for handling caudacoria is the average value obtained from three data points.
The AgF+HNO being diluted in AgNW inks3(CT1) dilution
Into AgNW suspension, addition fusion solution (FS) CT1 is replaced as described in table 11 below with part or all of
IPA diluents.The first sample without FS and HCl steams is used as fusion agent with served as control.Such as by the performance number in table 11
According to shown, when FS concentration is equivalent to coatings concentration (being used for the concentration of fusion solution being coated with the top of incomplete fusion network)
When, compared with control sample 1, similar resistance, TT and turbidity value are obtained in sample 5.Therefore, such as changed by the resistance of AgNW films
Enter to be proved, add a small amount of agglutinant contained in CT1 and seem to fuse AgNW really to form nanostructured network.Remove IPA
Diluent produces the result similar with the control of HCl steams.Fig. 6 a are the surfaces for the film for representing membrane sample 1 under different amplification
The composite diagram of the SEM image of collection and fusion or the sintering for showing nano wire.
Table 11
The AgNO being diluted in AgNW inks3+HNO3(CT2) dilution
Into AgNW suspension, addition fusion solution (FS) CT2 is replaced as described in table 12 below with part or all of
IPA diluents.The first sample without FS and HCl steams is used as agglutinant with served as control.Such as by the performance number in table 12
According to shown, when FS concentration is equivalent to coatings concentration, compared with control sample 1, similar resistance, TT are obtained in sample 5
And turbidity value.Therefore, proved as improved by the resistance of AgNW films, add a small amount of agglutinant contained in CT2 and seem certain
AgNW is fused to form nanostructured network.The method can potentially significantly reduce the turbidity of the film through processing because with tool
The film for having the extra coatings of sintering solution is compared, and only one coating is applied on substrate.For these solution, remove all
IPA diluents produce relatively low sheet resistance and compared with low turbidity relative to the control of HCl steams, and T% reduces slightly.Fig. 6 b are generations
The composite diagram of the SEM image gathered in table table 12 with the film surface of the CT2 films formed under different amplification, but the film
Sheet resistance be about 200 ohm-sqs.The notable sintering of Fig. 6 b displaying nano wires or fusion.
Table 12
The AgF (CT3) of filtering
The fusion solution (FS) only containing 0.01 weight % to 0.1 weight %AgF and anacidity is added into AgNW suspension
CT3 is with partly or entirely IPA diluent of the replacement as described in table 13 below.The first sample without FS and HCl steams is used
Make fusion agent with served as control.It is and right when FS concentration is equivalent to coatings concentration as shown in the performance data in table 13
Product 1 are compared in the same old way, and similar resistance, TT and turbidity value are obtained in sample 5.Therefore, demonstrate,proved as improved by the resistance of AgNW films
It is bright, add a small amount of fusion agent contained in CT3 and seem to fuse AgNW really to form nanostructured network.However, in relatively low CT3
Under ratio, fusion does not occur for one hour afterwards in coating.After 1 hour in sample after with mixed solution coated substrate
Observed in 5 compared with low resistance.It should be noted that without added acid in the system, AgF is separated out 30 minutes after coating.
Table 13
11 two kinds of ink solution fusions of example
Two kinds of ink solution sintering systems have been developed and have been showed in this example.Two kinds of ink solution sintering systems are
Following system:AgNW inks are used to form first coating, and different FS inks are used at the top of AgNW ink coatings
Form second coating.Exactly, propane diols (PG) is added in isobutanol (IBA), and wherein PG serves as reducing agent.With
EtOH or IPA systems are compared, and the IBA in two kinds of inking systems has higher and viscosity higher, it is believed that this is produced evenly
Coating.However, being different from EtOH, IBA is not easy to reduce Ag+, therefore PG is added to strengthen the reducing power of this system.Ink
AgNW concentration with 0.01 weight % to 0.5 weight %.All films are made in PET sheet, the PET sheet has about
0.3 to 0.4 turbidity and about 93.0 to 93.3 TT% (including PET substrate).
It is in 90 that the solution 1-4 listed in table 14 below, which is used,:The IBA and PG of 10 ratios admixture solvent are made.Collect flat
Equal 9 resistance datas point, and resistance data shown in table 14 is the average value of this 9 data points.Film without fuse process
Resistance>20,000 ohm-sqs.As shown in table 14 below, after fuse process, it was observed that with high TT and low turbidity
The resistance of all samples substantially reduces.
Table 14
Solution numbers | Sinter solution | Ohm-sq | TT%/turbidity |
1 | 1.6μL/mL HNO3+0.1mg/ml AgNO3 | 110 | 91.1/1.24 |
2 | 1.6μL/mL HNO3+0.1mg/ml AgF | 145 | 91.7/1.07 |
3 | 0.16μL/mL HNO3+0.1mg/ml AgNO3 | 181 | >90.0 |
4 | 0.16μL/mL HNO3+0.1mg/ml AgF | 69 | 90.8/1.46 |
Example 12 uses the IBA solution inks of organic reducing agent
A kind of inking system system is by the way that various reducing agents are added in IBA inks to be formed with small amount.Table 15 provides
It has been illustrated in a series of reducing agents that fusion is provided in a kind of inking system.These reducing agents in terms of reduction intensity it is different simultaneously
And there can also be other interesting properties.For example, during oxidation, reducing agent can change color, can be with
Improve the turbidity of whole film.
Table 15
The sample solution 1-6 listed in table 16 below is made with IBA and various reducing agents.Collect average 6 to 9 resistance numbers
Strong point, and resistance data shown in table 16 is the average value of this 6 to 9 data points.Film without sintering processes is by AgNW ink
Water is formed, and the AgNW inks include 0.01-0.5 weight %AgNW in IBA, and the resistance of film>20,000 ohm/flat
Side.Fuse film formed by using blade coating in the AgNW film coated thereons FS of deposition thin layer (about 50 μm moistening thickness) and
Then it is dried.As shown in table 15 below, after fuse process, it was observed that the sample containing styrax and amino-phenol
Resistance substantially reduces.Under additional reducing agent, other higher solvents can also be used.
In general, the film after fuse process shows high TT and low turbidity.During drying, Ag is concentrated+And reducing agent,
And Ag+It is reduced into metal Ago.The result of CT3 reducing agents is used in Case-based Reasoning 10, it is contemplated that receive even if fluorine ion can lure into
Rice noodles sinter, and AgF salpeter solutions also individually effectively will not significantly fuse nano wire in the case of without reducing agent.
Table 16
Sample | Isobutanol solution | Ohm-sq | TT% |
1 | 0.1mg/ml AgF, 1.6 μ L/mL HNO3, 0.17mg/ml styraxes | 62 | 90.7 |
2 | 0.5mg/ml AgF, 8 μ L/mL HNO3, 0.85mg/ml styraxes | 288 | >90.0 |
3 | 0.5mg/ml AgF, 8 μ L/mL HNO3, 0.17mg/ml styraxes | 144 | >90.0 |
4 | 0.5mg/ml AgF, 8 μ L/mL HNO3, 0.35mg/ml EPBP | 179 | >90.0 |
5 | 0.5mg/ml AgF, 8 μ L/mL HNO3, 0.20mg/ml AHNS | 457 | >90.0 |
6 | 0.5mg/ml AgF, 8 μ L/mL HNO3, 0.1mg/ml amino-phenols | 138 | 92.3 |
AFM with the film (sample 1) sintered based on benzoic solution is drawn in Fig. 6.As shown in Figure 7, grow
Preferentially in rough region and strong with the interaction of seed nuclei and formed at the minimum region of barrier.Be grown on PET present by
Suppress, this because AgNW surface energy far above PET but it is reasonable.
Above example is intended to be illustrative and be not restrictive.Other embodiments are in claims.Though in addition,
The present invention so is described by reference to specific embodiment, but those skilled in the art will realize that can be without departing from the present invention
Spirit and scope under be changed in form and details.Any be incorporated to of document above by reference is all restricted, and makes
Obtain to be incorporated to and run counter to herein the clearly theme of disclosure.
Claims (50)
1. a kind of method for forming fusion metal Nano structure network, methods described include:
Metal nanometer line is set to be contacted with the fusion solution comprising reducing agent source and metal ion source so that metal ion to be reduced
Into its respective metal element, so as to the metal nanometer line be fused together to form the fusion metal Nano structure net
Network, wherein the fusion metal Nano structure network has at least 80% total transmittance of light from 400nm to 700nm.
2. according to the method for claim 1, wherein the metal ion from the metal ion source includes and institute
State the metallic element identical metallic element of metal nanometer line.
3. method according to claim 1 or 2, wherein the metal ion source include the metal from dissolving salt from
Son, and wherein described metal ion includes the metallic element different from the metallic element of the metal nanometer line.
4. according to the method for claim 1, it is further included by removing the molten of the fusion solution at least in part
Agent concentrates the fusion solution, so as to realize the reduction of the metal ion and the fusion of the metal nanometer line.
5. the method according to claim 1 or 4, wherein the fusion solution includes acid.
6. according to the method for claim 5, wherein the fusion solution is free of additional metal composition, and the acid can
With effectively by the part ionization of the metal nanometer line to be used as the metal ion source.
7. the method according to claim 1 or 4, wherein the contact procedure, which is included on substrate, forms metal nanometer line
Film, and the fusion solution is applied to form the fusion metal Nano structure network to the metal nanowire film.
8. according to the method for claim 7, wherein the fusion solution is applied in into only the one of the metal nanowire film
Above part, to form patterning fusion metal Nano structure network over the substrate, wherein the contact portion is thin
Layer resistance ratio is small at least 10 times without the sheet resistance of the part of the fusion solution contact.
9. the method according to claim 1 or 4, wherein the fusion solution further includes metal nanometer line, and institute
The method of stating, which is further contained on substrate, deposits the fusion solution to form film, and the film dried at least in part with
Form the fusion metal Nano structure network.
10. the method according to claim 1 or 4, wherein the metal nanometer line includes silver.
11. according to the method for claim 10, wherein the metal ion source includes the metal ion from dissolving salt,
Wherein described metal ion include silver ion, copper ion, palladium ion, gold ion, tin ion, iron ion, cobalt ions, zinc ion,
Aluminium ion, platinum ion, nickel ion, titanium ion or its combination.
12. the method according to claim 1 or 4, wherein the fusion metal Nano structure network support on substrate with
Film is formed on the surface of the substrate.
13. according to the method for claim 12, wherein the sheet resistance of the film is not more than 300 ohm-sqs, and always
Transmission of visible light is at least 91%.
14. according to the method for claim 12, wherein the turbidity of the film is not more than 0.8%.
15. according to the method for claim 12, wherein the sheet resistance of the film is not more than 100 ohm-sqs.
16. according to the method for claim 12, wherein the fusion metal Nano structure network over the substrate negative
It is 0.01mg/m to carry density2To 200mg/m2。
17. according to the method for claim 12, it further comprising flushing and dries the film.
18. according to the method for claim 12, it further includes along selected pattern and removes the fusion metal nano
A part for structural network fuses nanostructured network to form patterning.
19. according to the method for claim 18, wherein the part for removing the fusion metal Nano structure network
Comprising applying etching solution corresponding to the selected pattern.
20. according to the method for claim 18, wherein the part for removing the fusion metal Nano structure network
Comprising being degraded with radiation to remove a part for the fusion metal Nano structure network, so as to form the patterning fusion gold
Belong to nanometer line network.
21. the method according to claim 1 or 4, it, which is further contained in, makes the fusion solution and the metal nano
Before linear contact lay, metal nanowire film is deposited on substrate surface, and degrades a part for the metal nanowire film, its
Middle patterning fusion nanostructured network is formed after the contact procedure.
22. a kind of solution group for sequentially applying, it is included:
Nano wire ink, it includes the dispersion liquid of metal nanometer line;With
Solution is fused, it includes metal ion source and reducing agent, and the metal ion source includes metal ion and/or oxidation
Agent, if wherein the metal ion is present, the metal ion is 0.00001M to 0.1M concentration, and wherein described fusion
Solution can effectively fuse the film of the metal nanometer line when drying.
23. solution group according to claim 22, wherein the oxidant is the strong of at least 0.000001M comprising concentration
Acid.
24. solution group according to claim 22, wherein the oxidant includes nitric acid.
25. the solution group according to any claim in claim 22 to 24, wherein the fusion solution is substantially not
Containing halide anion.
26. the solution group according to any claim in claim 22 to 24, wherein the reducing agent includes methanol, different
Propyl alcohol, n-butyl alcohol, 2- butanol, isobutanol, 2,3-butanediol, oxyacetone, propane diols or its combination, and wherein described solvent is
Reducing agent.
27. the solution group according to any claim in claim 22 to 24, wherein the reducing agent includes ethanol.
28. the solution group according to any claim in claim 22 to 24, wherein the reducing agent can be by described in
Metal ion is reduced into its respective metal element.
29. the solution group according to any claim in claim 22 to 24, wherein the reducing agent include oxyacetone,
Alpha-hydroxyacetophenone, phenol, amino-phenol, quinhydrones, pyrogallol, 4- amino -3- hydroxyls -1-naphthalene sulfonic aicd, catechol, Fei Ni
Ketone, azanol, sugar alcohol, monosaccharide and disaccharide, styrax, furoin, oxyacetone, phthalylhydrazine, adipic dihydrazide, 1- methyl-
1,4- cyclohexadiene, dihydro diazine, sulphite, bisulfites, thiosulfate, phosphite, phosphorous acid hydrogen salt, oxalic acid
Salt or its combination.
30. the solution group according to any claim in claim 22 to 24, wherein the metal ion include silver from
Son.
31. the solution group according to any claim in claim 22 to 24, wherein the metal ion source includes
Metal salt, the metal salt include the metallic element different from the metallic element of the metal nanometer line.
32. the solution group according to any claim in claim 22 to 24, wherein the nano wire ink includes extremely
Few 0.01 weight % metal nanometer lines.
33. the solution group according to any claim in claim 22 to 24, wherein the metal nanometer line include copper,
Gold, indium, tin, iron, titanium, platinum, palladium, nickel, cobalt or its alloy combination.
34. the solution group according to any claim in claim 22 to 24, wherein the metal nanometer line includes silver.
35. the solution group according to any claim in claim 22 to 24, wherein the average diameter of the nano wire
It it is at least 5 microns no more than 75nm and length.
36. the solution group according to any claim in claim 22 to 24, wherein the metal ion source includes
The acid of the metal ion from the metal nanometer line can be dissolved.
37. a kind of solution for being used to form conductive fusion metal Nano structure network, the fusion solution include metal nanometer line,
Metal ion source and reducing agent, the metal ion source include metal ion and/or oxidant.
38. the solution according to claim 37, wherein the oxidant is at least 0.000001M strong acid comprising concentration.
39. the solution according to claim 37 or 38, wherein the metal nanometer line includes nano silver wire, and the gold
Category ion source includes dissolving salt, and the dissolving salt includes the metal ion of the element different from silver.
40. the solution according to claim 37 or 38, wherein the metal nanometer line includes nano silver wire, the metal from
Sub- source includes the metal salt of dissolving, and the solution includes reducing agent and oxidant, wherein the reducing agent includes alcohol simultaneously
And the oxidant includes acid.
41. the solution according to claim 37, wherein the solution includes the gold with the concentration from 0.00001M to 0.1M
Belong to ion.
42. one kind fusion metal Nano structure network, it includes fusion metal nanometer line fragment, and formation is substantially free of halogen
Conductive network, wherein the fusion metal Nano structure network has at least 80% total transmission of light from 400nm to 700nm
Rate,
Wherein described fusion metal nanometer line fragment includes the first metal, and it is with identical or different with first metal second
Metal alloying with formed it is described fusion metal Nano structure network.
43. nanostructured network according to claim 42, wherein the metal nanometer line fragment include silver, copper, gold,
Indium, tin, iron, titanium, platinum, palladium, nickel, cobalt or its alloy combination.
44. a kind of material, it includes nanostructured network according to claim 42 and is supported by the nano junction above
The substrate of network forming network.
45. material according to claim 44, wherein the substrate includes glass, polymer, inorganic semiconductor material, nothing
Electromechanical dielectric material, its laminates, its compound or its combination.
46. the material according to claim 44 or 45, wherein the substrate include polymethyl methacrylate, polyolefin,
Polyvinyl chloride, fluoropolymer, polyamide, polyimides, polysulfones, polysiloxanes, polyether-ether-ketone, polyester, polystyrene, poly- amino
Formic acid esters, polyvinyl alcohol, polyvinyl acetate, acrylonitrile-butadiene-styrene copolymer, makrolon, its copolymer or its
Admixture.
47. the material according to claim 44 or 45, wherein the substrate include polyethylene terephtalate,
PEN PEN, polyacrylate or polynorbornene.
48. material according to claim 44, its sheet resistance is not more than 300 ohm-sqs, and its total visible ray is saturating
The rate of penetrating is at least 91%.
49. the material according to claim 44 or 48, its turbidity is not more than 0.8%.
50. the material according to claim 44 or 48, wherein the fusion metal Nano structure network is over the substrate
Load density be 0.01mg/m2To 200mg/m2。
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